JP2000026517A - Catalytic system for producing olefin (co)polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalytic system of low chlorine content, useful for producing an olefin (co)polymers in thigh yield by including an organoaluminum compound, a specific metal compound and a specific effective reactivator in specified proportions. SOLUTION: This catalytic system is obtained by including (A) an organolauminum compound such as ethylaluminum sesquichloride, (B) a compound of subgroup IV or VI metal (e.g. VOCl3), and (C) a mono- or dihalocarboxylic alkyl ester of the formula (X is a 1-6C alkyl or 1-6C alkoxy; Y is Cl, Br or H; Z is Cl or Br; R is a 1-6C alkyl) (e.g. methyl methoxydichloroacetate) as a reactivator, in the molar ratio C/B of 0.5-100. This catalytic system is useful for producing (co)polymers each from at least one α-olefin and a diene having nonconjugated double bond as necessary or conjugated diene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound comprising a) an organoaluminum compound, b) a compound of a metal of subgroup IV or VI of the periodic table, and c) a molar ratio of 0.5 to 100 with respect to the compound b). Containing a reactivating agent of the formula

[0002]

Embedded image Wherein, X is C ₁ ~ ₆ alkyl or C ₁ ~ ₆ alkoxy group, Y is Cl, Br, or H, Z is Cl or B
is r, and R using a mono- or Jiharokarubon acid alkyl esters of a a] C ₁ ~ ₆ alkyl group, a catalyst system, as well as the catalyst system, one or more α- olefins and optionally a non-conjugated double The present invention relates to a process for producing a (co) polymer by (co) polymerization from a diene or a conjugated diene having a heavy bond, and a polymer which can be produced using the catalyst of the present invention.

It is known to polymerize ethylene with other α-olefins and optionally with non-conjugated dienes, or homopolymerize olefins or conjugated dienes in the presence of mixed organometallic (Ziegler-Natta) catalysts. [Dictionary of Polymerization Science and Engineering (Encycl. Polym. Sci. En)
g. ), 2nd edition, Volume 6, 522 pages,
(Wiley, New York), 1986].
The polymerization is carried out in solution, as a suspension, or in the gas phase. The catalyst used is such that a transition metal compound of the subgroup IV or VI of the periodic table (normally a vanadium compound having a valence of +3 to +5) is used in common with an organometallic compound of the main group I to III (commonly an organic aluminum compound). You. Such catalyst systems exhibit very high initial activity, but have a sharp drop in activity as the transition metal is rapidly reduced to a low valence state (eg, +2) which is inert for polymerization purposes. . Therefore, in order to increase the yield of the polymer (for example, the amount of polymer in g units formed per g of transition metal), the transition metal compound is reoxidized, and its valence is changed to an active state for the purpose of polymerization. A returning reactivator is used.

The most effective reactivators for vanadium-containing catalysts are those containing chlorine. Polychlorinated compounds such as trichloroacetic acid esters (DE 157
0726), perchlorinated crotonic acid (German Patent No. 15
95442) or hexachlorocyclopentadiene (German Patent 1,495,698) have proven to be effective in practice. However, these reactivators have the disadvantage that the resulting copolymers exhibit a very high chlorine content. This chlorine content has a negative effect on the properties of many polymers, mainly aging resistance. Furthermore, polymers containing chlorine increase the corrosion of plant parts and the processing plant during the treatment of the polymer after polymerization. Compounds with a low chlorine content, such as mono- and dichloromalonic esters (CA272857, DE 2344267), usually show low activity. This effectively reduces the solids content in the polymer solution. To remedy this drawback,
Reactivators require disproportionately large amounts of vanadium compounds, which is an economic drawback. Effective compounds with a lower chlorine content have recently been disclosed as reactivators, for example dichlorophenyl acetate (EP 0044595). However, even when using such a reactivator, the chlorine content in the polymer must be reduced to the required low value using costly polymer washing.

[0005] EP 0680976 discloses the use of arylhalomalonates as reactivators for Ziegler-Natta catalysts containing vanadium. Although these compounds are certainly more effective than dichlorophenyl acetate, twice the amount of reactivator must be used to achieve satisfactory yields.

[0006] It is therefore an object of the present invention to provide at least one α-activator comprising a reactivating agent which does not exhibit the disadvantages of the prior art.
It is an object of the present invention to provide a catalyst system for the (co) polymerization of olefins and optionally dienes or conjugated dienes having non-conjugated double bonds.

The object of the present invention is to provide, according to the present invention, a) an organoaluminum compound, b) a compound of a subgroup IV or VI metal of the Periodic Table, Containing an activator, but with the formula

[0008]

Embedded image Wherein, X is C ₁ ~ ₆ alkyl or C ₁ ~ ₆ alkoxy group, Y is Cl, Br, or H, Z is Cl or B
is r, and R using a mono- or Jiharokarubon acid alkyl esters of a a] C ₁ ~ ₆ alkyl group is accomplished by providing a catalyst system.

The group R is a straight-chain or branched-chain or cyclic alkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl.
-Butyl, tert-butyl, n-pentyl, i-pentyl, n-hexyl, cyclopropyl, or cyclohexyl.

Residue Z may be Cl or Br. Cl
Is preferred.

Residue Y is H, Cl, or Br. If Y is Cl or Br, then Y = Z. Y is preferably Cl, since the alkyl dichlorocarboxylate has a higher activity or a lower price than the alkyl monochlorocarboxylate or the alkyl mono- or dibromocarboxylate, respectively.

The molar ratio of reactivator / transition metal is 0.5
-100, preferably 1-40.

The general formula X _y AlR _{3-y wherein} X is halogen and R is 1-6 carbon atoms.
And y is 0, 1 or 2] can be preferably used as the organometallic compound a) of the catalyst system. Examples of the alkyl group include methyl, ethyl, n
-Propyl, i-propyl, n-butyl, i-butyl,
sec-butyl, tert-butyl, n-pentyl or n-hexyl can be considered. Compounds that may be mentioned by way of example are ethylaluminum sesquichloride (ethyla).
luminium sesquichloride),
Ethyl aluminum dichloride, diethyl aluminum chloride, and diisobutyl aluminum chloride.
The compounds can be used alone or as a mixture.

[0014] Transition metal compounds of subgroups IV or VI of the periodic table can be used as transition metal compounds b), but vanadium compounds are particularly preferred. This compound in preferably the general formula X _y MR _3-y [wherein, M is V or VO, R is acetylacetonate - a preparative group or C ₁ ~ ₆ alkoxy group, also y is 1
Or 3]. Linear or branched alkoxy groups are, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
It can be considered as an alkoxy group such as sec-butoxy, tert-butoxy, n-pentyloxy or n-hexyloxy.

For example, VCl ₃ , VOCl ₃ , vanadium trisacetylacetonate, vanadyl bisacetylacetonate, alkyl vanadate having 1 to 6 carbon atoms and the like can be used. The compounds can be used alone or as a mixture.

Compounds containing vanadium in the oxidation state +4 are more preferred, and VCl ₄ is very particularly preferred.

The molar ratio of the organometallic compound / transition metal compound is from 1 to 100, preferably from 2 to 50.

The olefins which can be polymerized with the catalyst system according to the invention are preferably ethylene or C3-C10.
Α-olefins such as propylene, 1-butylene,
It is isobutylene, isoprene, 1-pentene, 1-hexene, 1-octene or 1-decene. Ethylene, propylene, isoprene and isobutylene are preferably used. When preparing copolymers from ethylene, other α-olefins and optionally dienes, propylene is preferably used as the second olefin (EPDM rubber). In this case, the ethylene content of the copolymer is in each case from 25 to 85% by weight, preferably from 40 to 75% by weight, based on the copolymer.

[0019] In many copolymers, unsaturated side chains are required for vulcanization. For this purpose, a non-conjugated diene, preferably 5-ethylidene-2-norbornene, dicyclopentadiene or 1,4-hexadiene is used as the third monomer. The concentration of the third monomer in the copolymer is 1 to 15% by weight, preferably 1 to 10% by weight, based on the copolymer.

For producing butyl rubber by polymerizing isobutylene with isoprene, preferably a catalyst system may also be used. The proportion of isoprene in the copolymer is preferably from 0.5 to 5% by weight.

Another preferred use of the catalyst system according to the invention is the production of polybutadiene by the polymerization of butadiene. Chain transfer agents such as hydrogen, ammonia, amines, dialkyl zinc, alkyl halides, acetylene hydrocarbons and the like can be used to control the molecular weight.

The (co) polymerization reaction is carried out in solution, in suspension,
Alternatively, it is performed in the gas phase. This method is well known to those skilled in the art, and details thereof are described in, for example, Ullman's Dictionary of Technical Chemistry, Volume A23, pages 290 et seq., Volumes A21, 35
9 pages, 18 volumes, 740 pages and 13 volumes, 60
Found on one page.

The solution (co) polymerization, an inert solvent such as an alkane (butane, pentane, hexane, C ₆ fraction, heptane and the like) or an aromatic (benzene, toluene) or in a liquid olefin, -90～100 ° C., Preferably 20-8
Proceed at a temperature of 0 ° C.

The suspension (co) polymerization is preferably carried out without solvent and an excess of monomer, propylene in the case of EPDM, is used as reaction medium. In this case, the reaction medium may be in supercritical form. It can also be operated at very low temperatures, for example at low temperatures up to -100 ° C., in halogenated hydrocarbons as solvents, for example dichloromethane or chloromethane.

The gas phase polymerization preferably proceeds with a supported vanadium catalyst or prepolymer. Regardless of the specific embodiment of the gas-phase polymerization, the claimed reactivators are also used here in order to increase the polymerization activity.

The (co) polymers obtained using the catalyst system according to the invention show that the organic compounds prepared from the reactivators according to the invention are chlorine-free after polymerization by hydrolysis in a stripper, but A very low halogen content is distinguished because the chlorine is instead removed in the form of HCl. H
Both Cl and organic compounds can be easily removed from the polymer by washing, or may remain in the polymer.

[0027]

The following examples and control examples illustrate the invention in more detail.

The reactivating agent according to the invention can be prepared according to the following examples.

Example 1 Preparation of methyl methoxydichloroacetate 100.0 g (0.847 mol) of dimethyl oxalate and 176.6 g (0.847 mol) of phosphorus pentachloride
Was heated to 130-135 ° C. in an oil bath for 18 hours while stirring in a 1 liter round bottom flask.

The resulting substantially colorless solution was rectified at about 10 mbar using a minimum length of 30 cm of a mirror-plated column. The product content of the fraction at about 60 ° C. and above 60 ° C. was examined using proton NMR and GC-MS.

The rectification is repeated once more, typically> 9
At a content of 0% a yield of 30-50% was achieved (GC-
MS: M-Cl, proton NMR: DMSO-d _6:
3.83 ppm, s, 6H).

Example 2.1 2-oxopropanoic acid 2-
Preparation of butyl ester 130 g (2 mol) of 2-oxopropanoic acid are combined with 200 g (2.7 mol) of 2-butanol and 7.5 g (40 mmol) of 4-toluenesulfonic acid in toluene 150 g.
Dilute with ml and heat to boiling. This device includes:
Equipped with a reflux condenser and a water separator. The mixture was refluxed until no more water separated.

Then, 300 ml of water were added, and the mixture was extracted three times with 100 ml each of diethyl ether. The combined organic phases were dried over anhydrous sodium sulfate and the ether was removed on a rotary evaporator. The residue was distilled under reduced pressure to obtain 210 g of the product.

Ester purity> 98% (determined by GC)
Met.

Example 2.2 Preparation of 2,2-dichloropropanoic acid 2-butyl ester 104.0 g (0.72 mol) of 2-oxopropanoic acid 2-butyl ester from Example 2.1 were treated with anhydrous tetrachloropropane. Dilute with 50 ml of methane and add anhydrous tetrachloromethane 3
To a boiling mixture of 260.3 g (1.25 mol) of PCl _{5 in} 00 ml was slowly added dropwise with stirring. Then, reflux was repeated for another 4 hours. Then, after replacing the reflux condenser, rectification was performed under reduced pressure using a distillation condenser. First the low-boiling components were removed at 40 ° C. and 150 mbar. The remaining reaction mixture was then transferred to a smaller distillation apparatus and rectified. 130 g of desired product (= 9
(0% yield). As determined by GC-MS, a small amount of 2-butyl 2-oxopropanoate and 2-butyl 2-chloroacrylate remained. However, no further processing was performed.

Example 2.3 Preparation of 2,2-dichloropropanoic acid 2-ethyl ester 424.8 g (2.04 mol) of phosphorus pentachloride was placed in 500 ml of anhydrous tetrachloromethane and heated to the boiling point.
Then 2-oxopropanoic acid 2- in 200 ml of CCl ₄
232.3 g (2.00 mol) of ethyl ester were added dropwise to the boiling mixture. The resulting mixture was refluxed for a further 3 hours, and the solvent was subsequently removed under reduced pressure. The residue was poured into ice water, and the resulting mixture was extracted three times with diethyl ether. The organic phase was washed with an aqueous 2% NaHCO ₃ solution and three times with water. After drying over magnesium sulfate, the solvent was removed once again under reduced pressure. 272.8 g of product (yield: 8
2%). According to NMR, the product consisted of 75% by weight of 2,2-dichloropropanoic acid 2-ethyl ester and 2-
It was found to consist of 25% by weight of chloroacrylic acid 2-ethyl ester. This mixture was used in Polymerization Example 4 without further purification.

Polymerization Example 1 (Control Example) The following component streams were distributed in a nominal 2 liter glass reactor: Hexane [Exxon Exxsol DHN50 by azeotropic distillation. Dry] 1833 g / h, ethylene 100 g / h, propylene 370 g / h and ENB 10 g / h. The reactor contents were adjusted to 2 liters. The pressure in the reactor was 7 bar, which was controlled using a safety valve on the gas phase part of the reactor and by continuous discharge of the product into the expansion vessel. Then, the temperature was maintained at 57 ° C. by cooling with a jacket. The catalyst components were fed as a hexane solution and the amount of hexane in the catalyst stream was taken into account to comply with the details given above: VOCl ₃ 0.035 g / h (0.2 mmol / h) EASC (ethylaluminum sesquichloride) 0.9
95 g / h (8.0 mmol / h) DCPAE 0.352 g / h (1.5 mmol / h).

Four hours after the start of the test, the polymer solution was
After collecting the time, the reaction was stopped with methanol, and the polymer was obtained by removing steam. 79 g of the product were obtained. 79MU
The Mooney value of (ML1 + 4, 125 ° C.) was measured. The composition was 45.3% by weight of propylene, 45.7% by weight of ethylene and 9.0% by weight of ENB.

Polymerization Example 2 (Control Example) The same procedure as in Polymerization Example 1 was repeated, except that 0.161 g / hour of nitropropane was used instead of DCPAE.

2.5% corresponding to the production of 47 g of polymer
Only the maximum concentration was obtained. No further treatment was performed as the formation of white streaks in the reactor indicated that it contained polyethylene.

Polymerization Example 3 (according to the invention) The same procedure as in Polymerization Example 1, except that 0.327 g / h (1.9 mmol) of methoxydichloroacetic acid methyl ester from Example 1 is used instead of DCPAE. Was used. In 1 hour, 88 g of a polymer having a composition of 41.3% by weight of propylene, 58.7% by weight of ethylene and 5.8% by weight of ENB and a Mooney viscosity of 78.2 were obtained. The solvent collected during removal was examined by GC. Methoxydichloroacetic acid methyl ester was no longer detected.

Polymerization Example 4 (According to the Invention) The following component streams were distributed in a nominal 2 liter glass reactor: hexane (Exol DHN50, anhydrous)
1.2 liters, 100 g of ethylene and propylene 3
70 g were introduced and the temperature was adjusted to 45 ° C. The pressure was 6 bar and the monomer was further fed as it was consumed.
The catalyst component was fed as a hexane solution, and the amount of hexane introduced was taken into account to comply with the above figures: VOCl ₃ 0.06 mmol EASC 1.7 mmol 0.04 product of example 2.3 Millimoles.

[0043] After 1 hour, water to terminate the polymerization by the addition of Irganox the polymer (Irganox ^R) 10
76 [Bayer AG] 0.3% by weight
And precipitated with ethanol and dried in a vacuum oven. 64.7% by weight of ethylene and 35.3% of propylene
40 g of EPR having a composition of% by weight were obtained.

Preparation Example 5 (Control Example) The same procedure was used as in Polymerization Example 4, except that 0.04 mmol of DCPAE was used instead of the product of Example 2.3. The temperature was 44 ° C.

62.2% by weight of ethylene and propylene 3
20 g of EPR having a composition of 7.8% by weight were obtained.

Comparing Polymerization Examples 4 and 5, it is clear that the production of the reactivating agent of the present invention is higher than that of DCPAE.

The features and aspects of the present invention are as follows.

1. a) an organoaluminum compound, b) a compound of a Group IV or VI subgroup metal of the periodic table, c) a reactivating agent having a molar ratio of 0.5 to 100 with respect to the compound b), provided that formula

[0049]

Embedded image Wherein, X is C ₁ ~ ₆ alkyl or C ₁ ~ ₆ alkoxy group, Y is Cl, Br, or H, Z is Cl or B
is r, and R using a mono- or Jiharokarubon acid alkyl esters of a a] C ₁ ~ ₆ alkyl group, a catalyst system.

2. Using 2-dichloropropanoic acid n-propyl ester or 2-methoxy-2,2-dichloroacetic acid methyl ester as a reactivating agent and having a valence of +3
The catalyst system of claim 1, wherein the vanadium compound of ~ + 5 is used as compound b).

3. Organoaluminum compound a) is wherein, X is halogen and R is C ₁ ~ ₆ alkyl, and y is 0, 1 or 2 is a general formula X _y AlR _3-y is the compound of , The catalyst system of 1 above.

4. In the formula X _y MR _3-y [wherein, M is V or VO, R is acetylacetonate - a preparative group or C ₁ ~ ₆ alkoxy group, also y is 1
Or 3) as the vanadium compound b).

5. Use of the catalyst system of 1 above for the production of a (co) polymer by (co) polymerization from one or more α-olefins and optionally a diene or conjugated diene having a non-conjugated double bond.

6. Use according to claim 5, wherein the copolymer produced is a copolymer of ethylene, at least one further α-olefin and optionally a diene with a non-conjugated double bond or a polymer of a conjugated diene.

7. Ethylene / propylene / diene rubber,
Use according to claim 5, for producing polybutadiene or butyl rubber.

8. A polymer which can be produced using the catalyst system according to the above item 1.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Johannes Rudolf Jansen Germany 40789 Monheim Kunitsplatter Schyutläs 47 (72) Inventor Thomas Esselt Germany 54149 Off-Ellert Felenberg 40 (72) Inventor Andreas Zatler Germany 40229 Deutsseldorf Germany Gryunabeke 48 (72) Inventor Jürgen Schneider Germany 50668

Claims (3)

[Claims] 1. a) an organoaluminum compound, b) a compound of a subgroup IV or VI metal of the periodic table, c) a reactivating agent in a molar ratio of 0.5 to 100 with respect to the compound b), As a reactivating agent, the formula Wherein, X is C ₁ ~ ₆ alkyl or C ₁ ~ ₆ alkoxy group, Y is Cl, Br, or H, Z is Cl or B
is r, and R using a mono- or Jiharokarubon acid alkyl esters of a a] C ₁ ~ ₆ alkyl group, a catalyst system. 2. The production of a (co) polymer of the catalyst system of claim 1 by (co) polymerization from one or more α-olefins and optionally a diene or a conjugated diene having a non-conjugated double bond. use. 3. A polymer which can be prepared using the catalyst system of claim 1.